Electroanalytical Techniques

By

Dr. S. B. Wategaonkar
Assistant Professor,
Department of Chemistry,
Kisan Veer Mahavidyalaya, Wai
 Electroanalytical Techniques

Electroanalytical techniques include a group of instrumental techniques like potentiometry, voltammetry, conductometry,
coulometry, electrogravimetry in all of those techniques there is interaction of electricity with matter and in all the above
mentioned techniques we measure the electrochemical properties like potential, current, charge etc with help of different
instruments like potentiometer, pH meter, conductometer, voltammeter etc,. The use of electrical measurements for
analytical purposes has found large range of applications including analytical, environmental monitoring, industrial quality
control & biomedical analysis.

Why Electroanalytical Chemistry?

Electroanalytical methods have certain advantages over other analytical methods. Electrochemical analysis allows for the
determination of different oxidation states of an element in a solution, not just the total concentration of the element.

Electroanalytical techniques are capable of producing exceptionally low detection limits and an abundance of
characterization information including chemical kinetics information. The other important advantage is its low cost.
 Instrumentation used in Electroanalytical Techniques (Electrochemical Cell)

Electrochemical Cell

Oxidation-reduction or redox reactions take place in electrochemical cells. There are two types of electrochemical cells.
Spontaneous reactions occur in galvanic (voltaic) cells; nonspontaneous reactions occur in electrolytic cells. Both types of
cells contain electrodes where the oxidation and reduction reactions occur. Oxidation occurs at the electrode termed
the anode and reduction occurs at the electrode called the cathode.

Electrodes & Charge

The interface through which electricity is exchanged with electrolyte solution is

called electrode. There are two types of electrodes anode & cathode. The anode of
an electrolytic cell is positive (cathode is negative), since the anode attracts anions
from the solution. However, the anode of a galvanic cell is negatively charged,
since the spontaneous oxidation at the anode is the source of the cell's electrons or
negative charge. The cathode of a galvanic cell is its positive terminal. In both
galvanic and electrolytic cells, oxidation takes place at the anode and electrons flow
Galvanic or Voltaic Cells:

The redox reaction in a galvanic cell is a spontaneous reaction. For this reason, galvanic cells are commonly used as batteries.
Galvanic cell reactions supply energy which is used to perform work. The energy is harnessed by situating the oxidation and
reduction reactions in separate containers, joined by an apparatus that allows electrons to flow. A common galvanic cell is the
Daniell cell, shown below.
Electrolytic Cells:The redox reaction in an electrolytic cell is nonspontaneous. Electrical energy is required to induce the
electrolysis reaction. An example of an electrolytic cell is shown below, in which molten NaCl is electrolyzed to form liquid
sodium and chlorine gas. The sodium ions migrate toward the cathode, where they are reduced to sodium metal. Similarly,
chloride ions migrate to the anode and are oxided to form chlorine gas. This type of cell is used to produce sodium and
chlorine. The chlorine gas can be collected surrounding the cell. The sodium metal is less dense than the molten salt and is
removed as it floats to the top of the reaction container.
Classification of Electroanalytical Techniques

Electrochemical methods may be split up into two major classes

Potentiometric and Amperometric

 In Potentiometry the electron transfer (ET) reaction is kinetically facile (superficial) and we measure the potential of
a Galvanic cell under conditions of zero current flow. The cell potential responds to changes in the activity of the
analyte species present in the solution in a well defined manner described by the Nernst equation. Indeed the cell
potential varies in a linear manner with the logarithm of the analyte activity.

 In Amperometry the kinetics of the ET reaction will have to be driven by an applied potential and so we measure the
diffusion controlled current flowing across the electrode/solution interface. This current is directly proportional to the
bulk concentration of the analyte present in the solution.
Potentiometry
Potentiometry

Potentiometry is a kind of electroanalytical techniques in that the potential difference of a solution between the two electrodes is
measured with the help of electrochemical cell without drawing any substantial current from the solution components. Here the
current is drawn from an external sources like battery or AC source i.e. electricity, that work in opposing order block the flow of
electricity in the circuit of the electrochemical cell due to polarization of electrolyte solution. The potential at the surface of
indicator electrode is then related to the concentration of one or more analytes based on Nernst equation that is called direct

potentiometry. For example the electrode potential reaction on the surface of an indicator electrode in general is shown as
below

Where “Ox” and “Red” denote the oxidized and reduced forms of a compound at the surface of indicator electrode, respectively
The number of electrons involved in the reaction is n. The potential of the electrode, E, follows the Nernst equation:

Where E0 is the standard electrode potential for the electrode reaction, R is the gas constant, T is the absolute temperature and F

is the Faraday constant. The activities of the species Ox and Red are denoted by a Ox and aRed, respectively.
Potentiometric titration
While in potentiometric titration after addition of each ml of volume increments of the standard solution to the analyte solution the potential
change of that solution is measured with the help of indicator electrode that is called potentiometric titration.
The potential at the surface of an indicator electrode inserted into the analyte solution can be measured by using an instrument called
electrochemical or galvanic cell.

Instrumentation of Potentiometry
A modified electrochemical cell is used in potentiometry for the measurement of potential difference of a solution between the two
electrodes without drawing any substantial current from the solution components.
The Electrochemical cell consist of
• Reference Electrode
• Salt bridge
• Indicator Electrode
• Potentiometer
• Electrolyte solution
The cell notation
Potentiometric cell
This electrochemical cell (Potentiometric cell) consists of two half-cells, one is called reference electrode half cell it
containing reference electrode whose potential is known, constant and independent of concentration of analyte. While the
other half-cell is called working electrode half cell whose potential is unknown, and change by varying the concentration of
analyte. It depends on analyte concentration. It also consist of potentiometer (or digital voltmeter) and salt bridge. The
potentiometer (rheostat) is a device that pushes back the current produced in the circuit due to chemical reaction and thus
minimizes the flow of current in the circuit so avoid the polarization of electrodes. It measure the amount of potential
produced at the surface of indicator electrode by comparing the known potential of the source connected with the
potentiometer. A salt bridge (i.e. filter paper soaked in KNO3) is often employed to provide ionic contact between two half-
cells with different electrolytes—to prevent the solutions from mixing and causing unwanted side reactions. As electrons
flow from one half-cell to the other, a difference in charge is established. If no salt bridge were used, this charge difference
would prevent further flow of electrons. A salt bridge allows the flow of ions to maintain a balance in charge between the
oxidation and reduction vessels while minimize the liquid junction potential. It maintains the electrical neutrality in each
half cell as ions flow into and out of the salt bridge.
Reference electrode

Reference electrode is that electrode whose potential is known, constant and does not change with electrode reaction. In
addition this electrode should be rugged and easy to assemble and should maintain a constant potential while passing
minimal currents.

There are three main types of reference electrodes which are commonly used

• Standard hydrogen electrode (SHE) (E=0.000 V) activity of H+=1

• Saturated calomel electrode (SCE) (E=+0.242 V saturated)

• Silver- Silver chloride electrode

Standard hydrogen electrode (SHE)

The SHE is the universal reference electrode for reporting relative half-cell potentials. It is a type of gas electrode and was
widely used in early studies as a reference electrode, and as an indicator electrode for the determination of pH values. The
SHE could be used as either an anode or cathode depending upon the nature of the half-cell it is used with.

The SHE consists of a platinum electrode immersed in a solution with a hydrogen ion concentration of 1.00M. The platinum
electrode is made of a small square of platinum foil which is platinized (known as platinum black). Hydrogen gas, at a
pressure of 1 atmosphere, is bubbled around the platinum electrode. The platinum black serves as a large surface area for
the reaction to take place, and the stream of hydrogen gas keeps the solution saturated at the electrode site with respect to
the gas. It is interesting to note that even though the SHE is the universal reference standard, it exists only as a theoretical
electrode which scientists use as the definition of an arbitrary reference electrode with a half-cell potential of 0.00 volts.
(Because half-cell potentials cannot be measured, this is the perfect electrode to allow scientists to perform theoretical
research calculations.) The reason this electrode cannot be manufactured is due to the fact that no solution can be
prepared that yields a hydrogen ion activity of 1.00M.
Standard hydrogen electrode (SHE)
The value is affected by ...
• temperature
• pressure of any gases
• solution concentration
Hydrogen electrode is based on the redox half cell:

2H+(aq) + 2e- → H2(g)

This redox reaction occurs at platinized platinum electrode. The

electrode is dipped in an acidic solution and pure hydrogen gas is
bubbled through it. The concentration of both the reduced form
and oxidized form of hydrogen is maintained at unity. That
implies that the pressure of hydrogen gas is 1 bar and the activity
of hydrogen ions in the solution is 1 molar. The activity of
hydrogen ions is their effective concentration, which is equal to
the formal concentration times the activity coefficient. Activity
coefficients are close to 1.00 for very dilute water solutions, but The standard hydrogen electrode (S.H.E.) is difficult
are usually lower for more concentrated solutions. to set up so it is easier to choose a more convenient
Pt | H2(g, 1.0 atm)|H+(aq, A= 1.0M) secondary standard which has been calibrated
against the S.H.E.
½ H2(g, 1.0 atm) = H+(aq, A= 1.0M) + e Eo = 0.000 V
Saturated Calomel Electrode (SCE)

The SCE is a half cell composed of mercurous chloride (Hg2Cl2, calomel) in contact with a mercury pool. These components
are either layered under a saturated solution of potassium chloride (KCl) or within a fritted compartment surrounded by the
saturated KCl solution (called a double-junction arrangement). A platinum wire is generally used to allow contact to the
external circuit. The half reaction is described by

Hg(l) | Hg2Cl2 (sat’d), KCl (sat’d) | |

electrode reaction in calomel hal-cell

Hg2Cl2 (s) + 2e = 2Hg(l) + 2Cl–
Eo = + 0.268V
E = Eo – (0.05916/2) log[Cl–]2 = 0.244 V
Temperature dependent
A calomel electrode saturated with KCl is called a saturated
calomel electrode, abbreviated S.C.E.
Advantage : using saturated KCl is that [Cl -] does not change if
some liquid evaporates.
The crystal structure of calomel(Hg2Cl2),
which has limited solubility in water
(Ksp = 1.8 ×10–18).

Hg2Cl2  Hg22+ + 2Cl–

Ksp = 1.8 ×10–18

Saturated KCl = 4.6 M KCl

. Silver/Silver Chloride (Ag/AgCl)

The silver/silver chloride reference electrode is composed of a silver wire, sometimes coated with a layer of solid silver
chloride, immersed in a solution that is saturated with potassium chloride and silver chloride. The pertinent half reaction is

AgCl (s) + e Ag (s) + Cl- (sat’d)

Ag(s) | AgCl (sat’d), KCl (xM) | |

AgCl(s) + e = Ag(s) + Cl–
Eo = +0.244V
E = Eo – (0.05916/1) log [Cl–]
E (saturated KCl) = + 0.199V (25oC)

The electrode has many features making is suitable for use in the field:
 Simple construction

 Inexpensive to manufacture

 Stable potential

 Non-toxic components
Indicator electrode

Indicator electrode is that electrode its potentional value depends on the concentration of analyte and the potentional
value at it surface changes with the change of concentration of analyte. There are two types of indicator electrodes i.e.
metallic indicator electrodes and Ion selective indicator electrodes.

Metallic indicator electrode: Metallic indicator electrodes are made of metals, there are three types of metallic indicator
electrodes i.e. 1st kind, 2nd kind, 3rd kind

1st kind metallic indicator electrodes:

These are made of the metal and used to determine the
potential of solution which containing the ion like the
electrode. These are not very selective, response to
other ion in the solution. Some metals (Cu, Zn, Cd)
dissolve in acidic solutions of Cu, Zn & Cd and other
examples are Ag, Hg, Bi, Tl, Pb
2nd kind Metallic Indicator electrodes: These metallic indicator electrode responses to the concentration of anion in the
solution i.e. Ag wire in AgCl saturated surface response to the chloride ion concentration. The other example is calomel
electrode which also response to anion i.e. chloride ion concentration in the solution
1) Silver-silver chloride electrode
Ag(s) | AgCl (sat’d), KCl (xM) | |
AgCl(s) + e = Ag(s) + Cl–
Eo = +0.244V
E = Eo – (0.05916/1) log [Cl–]
E (saturated KCl) = + 0.199V (25oC)

2) Calomal electrode
Hg(l) | Hg2Cl2 (sat’d), KCl (sat’d) | |
electrode reaction in calomel hal-cell
Hg2Cl2 (s) + 2e = 2Hg(l) + 2Cl–
Eo = + 0.268V
E = Eo – (0.05916/2) log[Cl–]2 = 0.244 V
Temperature dependent
A calomel electrode saturated with KCl is called a saturated calomel elec-
trode, abbreviated S.C.E.
Advantage : using saturated KCl is that [Cl -] does not change if some liquid
evaporates.
3rd kind Metallic Indicator electrodes: These metallic indicator electrode are made of inert metal like Pt, Au, Pd or carbon and response to
a mixture of ions like Fe2+/ Fe3+. Provides a surface for the electrochemistry to occur

Ion selective electrode (ISE)

Ion Selective Electrodes (ISE) are membrane electrodes that respond selectively to an ion in the presence of other ions. These include probes
that measure specific ions and gases in solution. The most commonly used ISE is the pH probe. Other ions that can be measured include
fluoride, bromide, cadmium, Silver, copper, lead, magnesium, calcium etc and gases in solution such as ammonia, carbon dioxide, and
nitrogen oxide.
The use of Ion Selective Electrodes in environmental analysis offer several advantages over other methods of analysis. First, the cost of
initial setup to make analysis is relatively low. The expense is considerably less than other methods, such as Atomic Adsorption
spectrophotometry or Ion Chromatography. ISE electrodes are good to use in color solution and are not subject to interferences such as color
in the sample. This makes them ideal for clinical use (blood gas analysis) where they are most popular; however, they have found practical
application in the analysis of environmental samples, often where in-situ determinations are needed and not practical with other methods.
A large number of ISE electrodes with good selectivity for specific ions are based on the measurement of the potential generated across a
membrane called membrane potential or boundary potential. The membrane is usually attached to the end of a tube that contains an internal
reference electrode. This membrane electrode and an external reference electrode are then immersed in the solution of interest. Since the
potentials of the two reference electrodes are constant, any change in cell potential is due to change in potential across the membrane.
Ion selective electrode (ISE)

There are five fundamentally different types of membrane which selectively interact with the ion or ions to be determined:
(1) glass membrane
(2) liquid membrane: (a) electrically charged ligand groups (ion exchangers) as membrane components
(3) solid-state membrane
(4) Gas sensing electrodes
(5) Enzyme electrodes

Selectivity coefficient
kX,Y = (response to Y) / (response to X)

General behavior of ISE

E = constant  (0.05916/nX) log [AX +(kX,Y AY nX nY )]
Glass membrane Electrode

Glass electrodes were the first ion-selective electrodes to become known. For
more than 60 years, they have been widely used for pH determinations in
solutions, both in industry and in scientific research, particularly in biology
and medicine. Usually, the electrodes are blown from glass called Corning 015
having chemical composition 22% Na2O, 6% CaO, and 72% SiO2, in the form
of bulbs having a wall thickness of about 0.1mm. Inside the tube are 0.1 M
solution of HCl and a saturated solution of silver chloride. A silver wire coated
with silver chloride is dipped into this solution to just have electrical contact
inside the thin membrane of the electrode. While this is almost the same
design as that of the silver–silver chloride reference electrode. See Figure
Glass membrane Electrode

The potential that develops at the surface of glass electrode is called

membrane potential. Since the glass membrane at the tip is thin, a potential
develops due to the difference in the concentration of the hydrogen ions on
opposite sides of the membrane that causes the potential—the membrane
potential—to develop. There is no half-cell reaction involved.

Ag(s) | AgCl[sat’d], Cl–(inside), H+(inside) | glass membrane | H+(outside)

The Nernst Equation
E = Eo – (0.05916/1) log [Cl–] + (0.05916/1) log ([H+(outside)]/[H+(inside)])
E = Q + (0.05916/1) log [H+(outside)]
or, since the internal [H+] is a constant, it can be combined with Eo, which is
also a constant, giving a modified Eo, E*, and eliminating [H+](internal)

In addition, we can recognize that pH = –log [H +] and substitute this into the
above equation
Mechanism of conduction
The conductivity of glass at room temperature is very low. It arises from the slight mobility of sodium ions in the
glass. In its usual form, glass does not contain hydrogen ions. However, during the leaching of glass in aqueous
solutions its surface layer is altered to a certain depth; water molecules enter, and hydration processes and some
swelling occur. Part of the sodium ions in the surface layer are leached out and are replaced by hydrogen ions from
the solution. Equilibrium is established between the hydrogen ions in the surface layer and those in solution; hence,
an equilibrium potential difference between the phases arises. The special feature of this surface layer is its
exceptionally high selectivity toward hydrogen ions (relative to sodium ions or other cations). For this reason, the
two sides of the membrane act as good hydrogen electrodes. As we know internal membrane of glass electrode
containing known number of hydrogen ions (a = 0.IM of H+) while the external membrane containing different. So
due to difference in number of hydrogen ions across the both sides of the glass membrane cause a positive charge
imbalance which is responsible for membrane potential.
SiO─ Na+ (solid) + H+ (solution) ↔ SiO─H+ (solid) + Na+ (solution)
The protons are free to move and exchange with other ions.
Potential is determined by external [H+]
Composition of glass membranes
70% SiO2
30% CaO, BaO, Li2O, Na2O,
and/or Al2O3

Ion exchange process at glass

membrane-solution interface: (a) Cross-sectional view of a silicate glass structure. In addition to the three
Si│O bonds shown, each silicon is bonded to an additional oxygen atom,
either above or below the plane of the paper. (b) Model showing three-
Gl– + H+ = H+Gl– dimensional structure of amorphous silica with Na + ion (large dark blue) and
several H+ ions small dark blue incorporated.
In contrast to other types of ion-selective membranes, the current between the two surface layers is transported across
the central part of the glass membrane by different ions, the sodium ions. Doping the glass membrane with different
proportions of aluminum oxide and other metal oxides can produce ion-selective glass membrane electrodes selective for
other metallic ions such as Li+, Na+, K+, Ag+ or NH4+.

Calibration or standardization of pH meter

The pH meter is standardized (calibrated) with the use of buffer solutions. Usually, two buffer solutions are used for
maximum accuracy. The pH values for these solutions should bracket the pH value expected for the sample. For example, if
the pH of a sample to be measured is expected to be 9.0, buffers of pH =7.0 and pH = 10.0 should be used. Buffers with pH
values of 4.0, 7.0, and 10.0 are available commercially specifically for pH meter standardization. Alternatively, of course,
homemade buffer solutions may be used. In either case, when the pH electrode and reference electrode are immersed in
the buffer solution being measured and the electrode leads are connected to the pH meter, the meter reading is
electronically adjusted (refer to manufacturer’s literature for specifics) to read the pH of this solution.

The electrodes can then be immersed into the solution being tested and the pH directly determined.
 Glass pH electrode
• Advantages over other electrodes for pH
measurements:
• Its potential is essentially not affected by the
presence of oxidizing or reducing agents.
• It operates over a wide pH range.
• It responds fast and functions well in
physiological systems.
• Selective for monovalent cations only
because polyvalent ions can not penetrate
the surface of membrane.
Errors that affect pH measurements with glass electrode

1. The alkaline(sodium) error : low readings at pH values greater than 9

2. The acid error : somewhat high when the pH is less than about 0.5
3. Dehydration may cause erratic electrode performance.
4. Variation in junction potential : ~ 0.01 pH unit
5. Error in the pH of the standard buffer :  0.01 pH unit

Cleaning glass electrode :

1. Washing with 6M HCl
2. 20 w/w% aqueous ammonium bifluoride (NH4HF2)
 LIQUID MEMBRANE ELECTRODE
• Liquid membrane is a type of ISE based on water- immiscible liquid
substances produced in a polymeric membrane used for direct
potentiometric measurement.
• Used for direct measurement of several polyvalent cations (Ca ion)
as well as a certain anions.
• Inner compartment of electrode contains reference electrode &
aqueous reference solution.
• Outer compartment – organic liquid ion exchanger
•The polymeric membrane made of PVC to separate
the test solution from its inner compartment which
contains standard solution of the target ion.
•The filling solution contains a chloride salt for
establishing the potential of the internal Ag/AgCl
wire electrode.
Liquid ISE
Ca ISE
Calcium didecylphosphate dissolved in dioctylphenylphosphonate

[(CH3(CH3)8CH2O)2PO2]2Ca  2[(CH3(CH3)8CH2O)2PO2]– + Ca2+

Diagram of a liquid-membrane electrode for Ca 2+.

Comparison of a liquid-membrane calcium ion electrode with a glass pH electrode.
Photograph of a potassium liquid-ion
exchanger microelectrode with 125 m of ion
exchanger inside the tip. The magnification
of the original photo was 400×.
A homemade liquid-membrane electrode.
Solid state crystalline membrane electrode

Migration of F– through LaF3 doped with EuF2.

Example: Fluoride (F-) electrode

Internal ref electrode

Ag/AgCl
Filling soln.
Aqueous NaCl + NaF
Membrane
LaF3 crystal disc
Applications
Electroplating industry, water treatment (fluoridation), toothpaste
 GAS SENSING ELECTRODE
• Available for the measurement of ammonia, carbon
dioxide and nitrogen oxide.
• This type of electrode consist of permeable
membrane and an internal buffer solution.
• The pH of the buffer changes as the gas react with it.
• The change is detected by a combination pH sensor.
• This type of electrode does not require an external
reference electrode.
 pco2 electrode
 Measurement of PCO2
in routine blood
gases
 A modified pH
electrode with a CO2
permeable
membrane covering
the glass membrane
surface
 A bicarbonate buffer
separates the
membranes
 Change in pH is
proportional to the
concentration of
Applications of ion selective electrodes
Ion-selective electrodes are used in a wide variety of applications for determining the concentrations
of various ions in aqueous solutions. The following is a list of some of the main areas in which ISEs
have been used.
Pollution Monitoring: CN, F, S, Cl, NO 3 etc., in effluents, and natural waters.
Agriculture: NO3, Cl, NH4, K, Ca, I, CN in soils, plant material, fertilisers and feedstuffs.
Food Processing: NO3, NO2 in meat preservatives.
Salt content of meat, fish, dairy products, fruit juices, brewing solutions.
F in drinking water and other drinks.
Ca in dairy products and beer.
K in fruit juices and wine making.
Corrosive effect of NO3 in canned foods.
Detergent Manufacture: Ca, Ba, F for studying effects on water quality.
Paper Manufacture: S and Cl in pulping and recovery-cycle liquors.
Explosives: F, Cl, NO3 in explosive materials and combustion products.
Electroplating: F and Cl in etching baths; S in anodising baths.
Biomedical Laboratories: Ca, K, Cl in body fluids (blood, plasma, serum, sweat).
F in skeletal and dental studies.
Education and Research: Wide range of applications.
 Application of Potentiometric
Measurement
• Clinical Chemistry
– Ion-selective electrodes are important
sensors for clinical samples because of
their selectivity for analytes.
– The most common analytes are
electrolytes, such as Na+, K+, Ca2+,H+, and
Cl-, and dissolved gases such as CO2.

• Environmental Chemistry
– For the analysis of of CN-, F-, NH3, and NO3-
in water and wastewater.
• Potentiometric Titrations
– pH electrode used to monitor the change in
pH during the titration.
– For determining the equivalence point of
an acid–base titration.
– Possible for acid–base, redox, and
precipitation titrations, as well as for
titrations in aqueous and nonaqueous
solvents.
• Agriculture
– NO3, NH4, Cl, K, Ca, I, CN in soils, plant
material, fertilizers.
• Detergent Manufacture
– Ca, Ba, F for studying effects on water
quality
• Food Processing
– NO3, NO2 in meat preservatives
– Salt content of meat, fish, dairy products, fruit juices,
brewing solutions.
– F in drinking water and other drinks.
– Ca in dairy products and beer.
– K in fruit juices and wine making.
– Corrosive effect of NO3 in canned foods.
 advantages
• Relatively inexpensive and simple to use and have an
extremely wide range of applications and wide
concentration range.
• Under the most favourable conditions, when measuring
ions in relatively dilute aqueous solutions and where
interfering ions are not a problem, they can be used
very rapidly and easily.
• ISEs can measure both positive and negative ions.
• They are unaffected by sample colour or turbidity.
• Non-destructive: no consumption of analyte.
• Non-contaminating.
• Short response time: in sec. or min. useful in
industrial applications.
 LIMITATION
• Precision is rarely better than 1%.
• Electrodes can be affected by proteins or other
organic solutes.
• Interference by other ions.
• Electrodes are fragile and have limited shelf
life.
Voltammetry
 Voltammetry

General Principles of Voltammetry

• In voltammetry diffusion current (I) is measured as a function of changing
potential (E)
• As potential is applied, electrolysis of analyte begins and current rises until it
reaches a limiting current

• The magnitude of this current is directly

proportional to the activity or concentration of
analyte i.e I = kC
• Where I= current, k = constant, C = concentration
of analyte
• E1/2 = half wave potential (characteristic of every
redox reaction) used for identification purposes
• Plot of I vs. E is called a voltammogram
Voltametric Cell
• Electrolytic cell consisting of 3 electrodes:
• Micro indicator electrode like Hg, Pt, Au, Ag, C or others
• Reference electrode like SCE or Ag/ AgCl
• Auxillary counter electrode like Pt wire
 Typical 3-electrode
Voltammetry cell

Reference electrode
Counter
electrode

Working electrode

O Reduction at electrode
O Causes current flow in
e- Mass transport External circuit

R R

End of Working electrode Bulk solution

Voltametric Cell
• Changing potential (E) is applied on indicator electrode (working
electrode) to drive a nonspontaneous redox reaction
• Counter electrode serves to conduct electricity between the two
electrodes
• Reference electrode has a constant potential throughout
• A supporting electrolyte is a salt added in excess to the analyte solution.
Most commonly, it is an alkali metal salt that does not react at the
working electrode at the potentials being used. The salt reduces the
effects of migration and lowers the resistance of the solution.
Three electrode cell:
• Working
• Reference
• Counter/auxilliar
current flows between working and counter
electrodes.
Potential controlled by potentiostat between
working and reference electrodes.
 Influence of applied potential on the faradaic current
• When the potential applied to the working electrode reaches to the
reduction potential of the electroactive species, a reduction will
take place at the electrode surface
• Thus, electroactive species diffuses from the bulk solution to the
electrode surface and the reduction products diffuse from the
electrode surface towards the bulk solution. This creates what is
called the faradaic current.
 0.001 M Cd2+ in 0.1 M KNO3 supporting electrolyte

Electrode become more and more

reducing and capable of reducing Cd 2+
All Cd2+ around the electrode has
Cd2+ + 2e-Cd
already been reduced. Current at
Current starts to be registered at the the electrode becomes limited by
i (A)
electrode the diffusion rate of Cd2+ from the
Working electrode is E½ bulk solution to the electrode.
no yet capable of Thus, current stops rising and
reducing Cd2+  levels off at a plateauid
Current at the working
only small residual
electrode continue to rise as
current flow through
the electrode become more
the electrode Base line
reducing and more Cd2+ around
the electrode are being of residual
reduced. Diffusion of Cd2+ current
does not limit the current yet

-0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4

V vs SCE
Current in Voltammetry
• When an analyte is oxidized at the working electrode, a
current passes electrons through the external electric
circuitry to the auxiliary electrode.
• This current flows from the auxiliary to the working
electrode, where reduc­tion of the solvent or other
components of the solution matrix occurs .
• The current resulting from redox reactions at the working and
auxiliary electrodes is called a faradaic current.
• Sign Conventions A current due to the analyte's reduction is
called a cathodic current and, by convention, is considered
positive. Anodic currents are due to oxidation reactions and
carry a negative value.
• The magnitude of the faradaic current is determined
by the rate of the resulting oxidation or reduction
reaction at the electrode surface.
• Two factors contribute to the rate of the
electrochemical reaction:
• the rate at which the reactants and products are
transported to and from the surface of the electrode
(mass transport)
• and the rate at which electrons pass between the
electrode and the reactants and products in the solution.
(kinetics of electron transfer at the electrode surface)
 Influence of Mass Transport on the Faradaic
Current
There are three modes of mass transport to and from the electrode
surface: diffusion, migration, and convection.
• Diffusion from a region of high concentration to a region of low
concentration occurs whenever the concentration of an ion or
molecule at the surface of the electrode is different from that in bulk
solution.
• Convection occurs when a mechanical means is used to carry
reactants toward the electrode and to remove products from the
electrode.
• The most common means of convection is to stir the solution
using a stir bar. Other methods include rotating the electrode and
incorporating the electrode into a flow cell.
• Migration occurs when charged particles in solution are attracted or
repelled from an electrode that has a positive or negative surface
charge.
• Unlike diffusion and convection, migration only affects the mass
transport of charged particles
• diffusion is the only significant means for the mass transport
of the reactants and products, the current in a voltammetric
cell is given by

where n is the number of electrons transferred in the redox

reaction, F is Faraday's constant, A is the area of the electrode,
D is the diffusion coefficient for the reactant or product, CbuIk
and Cx=o are the concentration of the analyte in bulk solution
and at the electrode surface, and  is the thickness of the
diffusion layer.
Diffusion current : Id is directly proportional to the concentra-
tion of the analyte.
Id = limiting current – residual current  [C]o
Influence of the Kinetics of Electron Transfer on the Faradaic Current

• When electron transfer kinetics at the electrode surface are

fast, the redox reaction is at equilibrium, and the
concentrations of reactants and products at the electrode are
those specified by the Nernst equation.
• Such systems are considered electrochemically reversible.
• In other systems, when electron transfer kinetics are
sufficiently slow, the concentration of reactants and products
at the electrode surface, and thus the current, differ from
that predicted by the Nernst equation. In this case the system
is electrochemically irreversible.
 Non faradic Currents
• Currents other than faradaic may also exist in an electrochemical
cell that are unrelated to any redox reaction.
• These currents are called nonfaradaic currents
• The most important example of a nonfaradaic current occurs
whenever the electrode's potential is changed.
• When mass transport takes place by migration negatively
charged particles in solution migrate toward a positively charged
electrode, and positively charged particles move away from the
same electrode.
• When an inert electrolyte is responsible for migration, the result
is a structured electrode‑surface interface called the electrical
double layer, or EDL,
• The movement of charged particles in solution, gives rise to a
short‑lived, nonfaradaic charging current.
• Changing the potential of an electrode
• causes a change in the structure of
• the EDL, producing a small charging current.
 Residual Current
• Even in the absence of analyte, a small current flows through an
electrochemical cell.
• This current, which is called the residual current, consists of two
components:
• a faradaic current due to the oxidation or reduction of trace
impurities,
• a charging current. it is the current needed to charge or
discharge the capacitor formed by the electrode
surface‑solution interface. This is called the condenser
current or charging current.
• It is present in all voltammetric
and polarographic experiments,
regardless of the purity of reagents.
Types of Voltammetry

Different kinds of Voltammetry

• Polarography
• Linear sweep and Cyclic Voltammetry
• Hydrodynamic Voltammetry
• Pulsed methods
• Stripping Voltammetry
• AC Voltammetry
 Polarography

• Jaroslav Heyrovský was the inventor of the polarographic method,

and the father of electroanalytical chemistry, for which he was
the recipient of the Nobel Prize. His contribution to
electroanalytical chemistry can not be overestimated. All modern
voltammetric methods used now in electroanalytical chemistry
originate from polarography.
• In polarography the working electrode is a dropping mercury
electrode (DME) or a mercury droplet suspended from a bottom of
a glass capillary tube.
• Analyte is either reduced (most of the cases) or oxidized at the
surface of the mercury drop.
• The current –carrier auxiliary electrode is a platinum wire.
• SCE or Ag/AgCl reference electrode is used.
• The potential of the mercury drop is measured with respect to the
reference electrode.
The DME is referred to as the working or
indicator electrode, it is made up of
mercury reservoir
connected to a capillary tube. The
capillary tube deliver mercury size of
about 1mm in diameter
(micro-electrode), the mercury drops
detach after every two seconds and as
such a fresh surface of mercury is
encountered such that the reaction at any
point in time does not depend on the past
history of
the electrode. This therefore, makes the
electrode reaction perfectly reproducible.
Also since it is
a micro electrode, the amount of current
carried is very low (0-15UA).
Typical electrochemical cell used in polarography
 Advantages and Disadvantages of the Dropping Mercury Electrode
Some of the advantages of dropping mercury electrode(DME) are as follows:
 Mercury form amalgam with most metals.
 Mercury has a high hydrogen overvoltage.
 It provides a smooth, fresh surface for the reaction.
 Each drop remains unaffected and does not become contaminated by the deposited metal.
 Diffusion equilibrium is readily established at mercury-solution interface.
Some of the disadvantages of dropping mercury electrode(DME) are as follows:
 It is poisonous so care should be taken in its handling.
 Surface area of a drop of mercury is never constant.
 Applied voltage produces changes in surface tension and hence change in drop size.
 Mercury has limited applications in analysis of more positive potential range.

Following care must be taken while using dropping mercury electrode:

 Pure and triple distilled mercury should be used in DME
 Tip of DME should be always immersed in water when not in use.
 Tip of DME should be cleaned by dipping in nitric acid.
 The DME assembly should be mounted vertical on a heavy stand to be free from vibrations.
 It is essential to use clean and dust free tubing while setting the DME.
• One serious limitation of the dropping electrode is
the ease with which mercury is oxidized: this
property severely limits the use of the electrode as
an anode. At potentials greater than about + 0.4 V,
formation of mercury(I) gives a wave that masks
the curves of other oxidizable species.
• In the presence of ions that form precipitates or
complexes with mercury(I), this behavior occurs at
even lower potentials. For example, in the Figure,
the beginning of an anodic wave can be seen at 0 V
due to the reaction
• 2Hg + 2CI- < === > Hg2CI2(s) + 2e-
• Incidentally, this anodic wave can be used for the
determination of chloride ion.
70
• Another important disadvantage of the dropping
mercury electrode is the nonfaradaic residual or
charging current, which limits the sensitivity of the
classical method to concentrations of about 10 -5 M.
• At lower concentrations, the residual current is
likely to be greater than the diffusion current, a
situation that prohibits accurate measurement of the
latter.
• Finally, the dropping mercury electrode is
cumbersome to use and tends to malfunction as a
result of clogging.

72
Polarography uses mercury droplet
electrode that is regularly renewed
during analysis.
Applications:
Metal ions (especially heavy metal
pollutants) - high sensitivity.
Organic species able to be oxidized
or reduced at electrodes: quinones,
reducing sugars and derivatives, thiol
and disulphide compounds,
oxidation cofactors (coenzymes etc),
vitamins, pharmaceuticals.
Alternative when spectroscopic
methods fail.
 SHAPE OF THE POLAROGRAM
A graph of current versus potential in a polarographic experiment
is called a polarogram.
Cd2+ + 2e Cd
Features of the Polarogram
• residual current – the small current before the potential at which
the analyte reacts, caused by reactive species in the matrix and by
the mercury drop behaving like a capacitor
• limiting current – the maximum current reached
• diffusion current – the difference between the limiting and
residual, and proportional to the concentration of analyte
• half-wave potential – the potential half-way up the polarographic
wave, which is similar to the reduction/oxidation potential, and
characteristic of the species;
• current oscillations – caused by the mercury drop which
repeatedly falls off and is replenished from the capillary
Polarographic Mechanism
• When the potential is only slightly negative with respect to the calomel
electrode, essentially no reduction of Cd 2+ occurs. Only a small residual
current flows.
• At a sufficiently negative potential, reduction of Cd 2+ commences and
the current increases. The reduced Cd dissolves in the Hg to form an
amalgam.
• After a steep increase in current, concentration polarization sets in: The
rate of electron transfer becomes limited by the rate at which Cd 2+ can
diffuse from bulk solution to the surface of the electrode.
• The magnitude of this diffusion current Id is proportional to Cd2+
concentration and is used for quantitative analysis. The upper trace in
the Figure above is called a polarographic wave.
• The oscillating current in the Figure above is due to the growth and fall
of the Hg drops.
• As the drop grows, its area increases, more solute can reach the surface
in a given time, and more current flows.
• The current increases as the drop grows until, finally, the drop falls off
• Current or rate of diffusion  [C]o - [C]s
The [C]o and [C]s are the concentrations in the bulk
solution and at the electrode surface.
• The greater the difference in concentrations the
more rapid will be the diffusion.
• At a sufficiently negative potential, the reduction is
so fast that the [C]s << [C]o and equation above
reduces to the form
• Limiting current = diffusion current  [C]o
• The ratio of the diffusion current to the bulk solute
concentration is the basis for the use of voltammetry
in analytical chemistry
• The magnitude of the diffusion current, is given by the Ilkovic
equation:
• ld = (7.08 x 104)nCD1/2 m 2/3 t 1/6
• where Id = diffusion current, measured at the top of the
oscillations in the Figure above with the units µA
• n = number of electrons per molecule involved in the
oxidation or reduction of the electroactive species.
• C = concentration of electroactive species, with the units
mmol/L
• D = diffusion coefficient of electroactive species, with the
units M2/s
• m =rate of flow of Hg, in mg/s
• t = drop interval, in s
• The number 7.08 x 104 is a combination of several constants
whose dimensions are such that ld will be given in , µA
• Thus, id is proportional to the concentration of a certain species
under specific conditions and the above equation may be
expressed as follows:
id = kc
• where k is constant under the specific conditions.
• If k is constant for a series of standard solutions of various
concentrations and an unknown, a calibration plot can be
constructed and the unknown concentration can be determined.
• Clearly, the magnitude of the diffusion current depends on
several factors in addition to analyte concentration.
• In quantitative polarography, it is important to control the
temperature within a few tenths of a degree.
• The transport of solute to the electrode should be made to occur
only by diffusion (no stirring).
Half-wave Potential, E1/2
• Half wave potential, E1/2 is an important feature can
be derived from the plarogram.
• It is the potential corresponding to one half the
limiting current i.e. id/2.
• El/2 is a characteristic for each element and thus used
for qualitative analysis.
 Supporting electrolyte
• Current flow due to electrostatic attraction (or
repulsion) of analyte ions by the electrode is reduced to
a negligible level by the presence of a high
concentration of supporting electrolyte (1 M HCl in the
Figure above).
• Increasing concentrations of electrolyte reduces the net
current, since the rate of arrival of cationic analyte at
the negative Hg surface is decreased.
• Typically, a supporting electrolyte concentration 50‑100
times greater than the analyte
concentration will reduce electrostatic transport of the
analyte to a negligible level.
Effect of Dissolved Oxygen

• Oxygen dissolved in the solution will be reduced at the DME

leading to two well defined waves which were attributed to
the following reactions:
• O2(g) + 2H+ + 2e- < ==== > H2O2; E1/2 = - 0.1V
• H2O2 + 2H+ +2e- < ==== > 2H2O; E1/2 = - 0.9V
• E1/2 values for these reductions in acid solution correspond to
-0.05V and -0.8V versus SCE.
• This indicates that dissolved oxygen interferes in the
determination of most metal ions.
• Therefore, dissolved O2 has to be removed by bubbling
nitrogen free oxygen into the solution before recording the
polarogram.
Current maxima

A distortion of the polarographic wave appears to be due

to absorption phenomena at the surface of the mercury
drop.

The maxima may be re-

moved by the addition of
surface active agent (max-
ima suppressors) such as
gelatine, methyl cellulose or
Triton X-100.
 Types of PolarograpicTechniques
Linear Sweep polarography or Direct Current (DC) polarography
• The earliest voltammetric experiment was normal polarography
at a dropping mercury electrode. In normal polarography the
potential is linearly scanned, producing Polarogram. In LSV the
major source of noise at low concentration is the capacitive
current resulting from charging of electrical double layer at the
electrode which limit the application of this technique to 10-5 M
Pulse polarography
By using pulse or differential pulse polarography, most of the
capacitive current can be eliminated with a resultant of increase in
the S/N ratio of about 100.
In pulse and differential pulse polarography advantage is taken of
the relatively rapid decrease in the capacitive current as compared
with faradic current after application of a potential to an electrode.
In pulse polarography a potential pulse is applied to the mercury
drop about 57ms prior to the drops fall from the capillary.
The capacitive current exponential decays to nearly zero during the
first 40ms of the pulse and the remaining faradic current is
measured during the last 17ms of the pulse.
A drop knocker is used to control time and to permit application of
the pulse just before the drop is knocked from the capillary.
It increase the sensitivity and the detection limits that are about 10
times lower then with low current.
 Differential Pulse Polarography
• In differential pulse polarography, the current is typically measured
during the 17ms prior to the application of the pulse and during the
last 17ms of application of the pulse and after decay of the capacitive
current. The polarogram is a plot of the difference between the two
currents as a function of the linearly increasing voltage.
• The drop is then mechanically dislodged.
• The current is not measured continuously. Rather, it is measured once
before the pulse and again for the last 17 ms of the pulse.
• The polarograph subtracts the first current from the second and plots
this difference versus the applied potential (measured just before the
voltage pulse).
• The resulting differential pulse polarogram is nearly the derivative of
a direct current polarogram, as shown in the Figure
• Again we have decreased the charging current and increased the
faradaic current. Generally, detection limits with differential pulse
polarography are two to three orders of magnitude lower than those
for classical polarography and lies in the range of 10-7 to 10-8 M.
Polarogram for a differential
pulse polarography experiment.
Here i = is2 – is1. The peak
potential, Epeak, is colsely
related to the polarographic
half-wave potential.
Square-wave polarography.
This is the same as the differential pulse method except we do not have
a continuous ramp of voltage but instead the potential is stepped as in
the picture.

The size of the pulses is such that the material reduced in the forward
pulse is oxidized in the reverse pulse. So we have little net consumption
of analyte. The detection limit for square-wave polarography is about
the same as for differential pulse – about 10 -7 to 10-8 M.

The advantage of the square-wave approach is the speed of the

measurement. With steps in the microseconds, an entire polarogram can
be obtained in 10 msec. The entire scan can be performed in the last
few msecs of the life of a single drop of mercury, when the charging
current is essential zero.

The speed of the measurement also permits increase in precision by

signal averaging data from a number of polarographic scans.
Square wave polarography
Square wave polarography is more sensitive and much faster than differen-
tial pulse polarography. The square wave is also better at rejecting back-
ground signals such as those generated by reduction of oxygen.

Waveform for square wave polarography.

 Square Wave Voltammetry

• advantage of square wave voltammetry is that the entire scan can be performed
on a single mercury drop in about 10 seconds, as opposed to about 5 minutes for
the techniques described previously. SWV saves time, reduces the amount of
mercury used per scan by a factor of 100. If used with a pre-reduction step,
detection limits of 1-10 ppb can be achieved, which rivals graphite furnace AA in
sensitivity.
•data for SWV similar to DPP
•height and width of the wave depends on the exact combination of
experimental parameters (i.e. scan rate and pulse height
Square-Wave Voltammetry

Reversible System
- The peak-shaped Polarogram is symmetric about the
half-wave potential

- Peak current is proportional to the concentration

- The net current is larger than the forward or reverse currents

Generation of a square-wave voltammetry excitation signal. The staircase signal in (a) is
added to the pulse train in (b) to give the square-wave excitation signal in (c ).
Current response for a reversible reaction to excitation signal.
Square-Wave Voltammetry

- Higher sensitivity than differential-pulse in which

reverse current is not used
(currents 4 times higher for reversible systems)
(currents are 3.3 times higher for irreversible systems)
- Low detection limits up to 10-8 M
- Reduced analysis time due to higher scan rates
(few seconds compared to ~3 minutes for differential pulse)
Entire Polarogram is recorded on a single mercury drop

- Effective Scan Rate = f∆Es

f = square-wave frequency

∆Es = step height

- May be used for kinetic studies

Cyclic Voltammetry (CV)
Cyclic voltammetry (CV) is an electrolytic method that uses microelectrodes and an
unstirred solution so that the measured current is limited by analyte diffusion at the
electrode surface. The electrode potential is ramped linearly to a more negative potential,
and then ramped in reverse back to the starting voltage. The forward scan produces a
current peak for any analytes that can be reduced through the range of the potential scan.
The current will increase as the potential reaches the reduction potential of the analyte, but
then falls off as the concentration of the analyte is depleted close to the electrode surface.
As the applied potential is reversed, it will reach a potential that will reoxidize the product
formed in the first reduction reaction, and produce a current of reverse polarity from the
forward scan. This oxidation peak will usually have a similar shape to the reduction peak.
The peak current, ip, is described by the Randles-Sevcik equation:
ip = (2.69x105) n3/2 A C D1/2 v1/2
where n is the number of moles of electrons transferred in the reaction, A is the area of the
electrode, C is the analyte concentration (in moles/cm 3), D is
The potential difference between the reduction and oxidation peaks is theoretically 59 mV
for a reversible reaction. In practice, the difference is typically 70-100 mV. Larger
differences, or nonsymmetric reduction and oxidation peaks are an indication of a
nonreversible reaction. These parameters of cyclic voltammograms make CV most suitable
for characterization and mechanistic studies of redox reactions at electrodes.
Cyclic voltammetry
In cyclic voltammetry, a periodic, triangular wave form is applied to the working elec-
trode. The portion between times to and t1 is a linear voltage ramp. In CV, the time is on
the order of seconds. The ramp is then reversed to bring the potential back to its initial
value at time t2.
Cyclic voltammetry is used principally to characterize the redox properties of com-
pounds and to study the mechanisms of redox reactions.

Waveform used in cyclic voltammetry. Cyclic voltammetric excitation signal.

Cyclic Voltammetry

• t0 → t1 : cathodic wave
• Instead of leaving off at the top of the
wave, current decreases at more
negative potential
← diffusion is too slow to replenish
analyte near the electrode
• t1 → t2 : anodic wave
• The potential is reversed and, reduced
product near the electrode is oxidized

2.22 RT 57.0
Epa  Epc   (mV) (at 25  C)
nF n Cyclic voltammograms are recorded either
with an osciloscope or with a fast X-Y
recorder.
The current decreases after the cathodic peak
because of concentration polarization.
For a reversible reaction, half-wave potential
lies midway between the cathodic and anodic
peaks.
(a) Potential vs time waveform and
(b) cyclic voltammogram for a solution that is
6.0 mM in K3Fe(CN)6 and 1.0M in KNO3.
 Fe(C5H5)2

5.375mM (left) and 0.5375 (right) mM Ferrocene in Acetonitrile

 Hydrodynamic Voltammetry

• In hydrodynamic voltammetry the solution is stirred by rotating the electrode.

• Current is measured as a function of the potential applied to a solid working
electrode.
• The same potential profiles used for polarography, such as a linear scan or a
differential pulse, are used in hydrodynamic voltammetry.
• The resulting voltammograms are identical to those for polarography, except for
the lack of current oscillations resulting from the growth of the mercury drops.
• Because hydrodynamic voltammetry is not limited to Hg electrodes, it is useful
for the analysis of analytes that are reduced or oxidized at more positive
potentials.
 Stripping Ansalysis

• Stripping analysis is an analytical technique that involves

• Preconcentration of a metal phase onto a solid electrode surface or into Hg
(liquid) at negative potentials and selective oxidation of each metal phase
species during an anodic potential sweep.
• The analyte from a dilute solution is first concentrated in a single drop of
Hg (or any micro-electorde) by electroreduction or electro-oxidation.
• The electroactive species is then stripped from the electrode by reversing
the direction of the voltage sweep.
• The potential becomes more positive, oxidizing the species back into
solution (anodic stripping voltammetry) or more negative reducing the
species back into solution (cathodic stripping voltammetry)
• The current measured during the oxidation or reduction is related to the
quantity of analyte
• The polarographic signal is recorded during the oxidation or reduction
process.
• The deposition step amounts to an electrochemical preconcentration of the
analyte; that is, the concentration of the analyte in the surface of the
microelectrode is far greater than it is in the bulk solution.
 Stripping Ansalysis

• Very sensitive and reproducible (RSD<5%) method for

• trace metal ion analysis in aqueous media.
• Concentration limits of detection for many metals are in
• the low ppb to high ppt
• range (S/N=3) and this compares
• favorably with AAS or ICP analysis.
• Field deployable instrumentation that is inexpensive.
• Approximately 12-15 metal ions can be analyzed for by
• this method.
• The stripping peak currents and peak widths are a
• function of the size, coverage and distribution of the
• metal phase on the electrode surface (Hg or alternate)
(a) Excitation signal for
stripping determination of
Cd2+ and Cu2+
(b) Voltamrnograrn.
Electrogravimetry
 Electrogravimetry
• In an electrogravimetric analysis, the analyte is
quantitatively deposited as a solid on the cathode or
anode.
– The increase in the mass of the electrode directly measures the
amount of analyte.
– Not always practical because numerous materials can be reduced
or oxidized and still not plated out on an electrode.

• Electrogravimetry can be conducted with or

without a controlled potential
• When No control
• A fixed potential is set and the electrodeposition
is carried out
• The starting potential must be initially high to
ensure complete deposition
• The deposition will slow down as the reaction
proceeds
• In practice, there may be other electroactive
species that interfere by codeposition with
the desired analyte.
• Even the solvent (water) is electroactive,
since it decomposes to H2 + 1/2O2 at a
sufficiently high voltage.
• Although these gases are liberated from the
solution, their presence at the electrode
surface interferes with deposition of solids.
• Because of these complications, control of
the electrode potential is an important
feature of a successful electrogravimetric
analysis.
 Examples on electrogravimetry

• Cu: is deposited from acidic solution using a Pt cathode

• Ni : is deposited from a basic solution
• Zn: is deposited from acidic citrate solution
• Some metals can be deposited as metal complexes e.g., Ag,
Cd, Au
• Some metals are deposited as oxides on the anode e.g.,
• Pb2+ as PbO2 and Mn2+ as MnO2
Coulometry
 Coulometric Methods of Analysis
Coulometric methods of analysis are based on the measurement of quantity of
electrical charge that passes through a solution during an electrochemical reaction.
The principle of coulometric method of analysis is governed by Faraday’s laws of
electrolysis.
Faraday’s First laws of electrolysis
According to the first law, the mass of a substance liberated at the electrodes during
electrolysis is directly proportional to the quantity of electrical charge (Q) that passed
through the electrolyte. m ∝ Q
Total charge, Q, in coulombs, passed during an electrolysis is related to the amount of
analyte by Faraday’s law
Q= N· F.n
Where Q is the amount of charge its unit is coulomb is equivalent to an A•s ; thus for a
constant current, I, the charge, Q, is given as, Q= I · t
coulombs = amperes · seconds
The charge on an electron is 1.6022 × 10–19 coulombs.
where F is Faraday constant charge carried by one mole of electrons, F=6.023x10 23 x
1.6022 × 10–19 = 96,487 C/mol and N is number of mole of analyte
 N = Q / n.F = I · t / n.F, as N=m/M.mass, so

where m is mass of analyte, M is molar

M • i .t mass, n, number of electron involved during
m= reaction and I is the amount of current and t is
n 96487
the time in second
Special Features of coulometric methods
1. Coulometric methods give more accurate and precise results than
classical methods since the electrical currents can be controlled and
measured with utmost precision.
2. These methods are suited for both routine as well as rare analyses which
involve electrolytic method of determination.
3. Coulometric titrations are more popular and have the special advantage in
the sense that the tedious steps of preparation, storage and handling of
standard titrants are avoided.
4. Titrations which cannot be performed by conventional methods can be
easily performed coulometrically. Titrations of high hazardous materials,
titrations involving unstable or difficulty prepared titrants such as
bromine, tin(II), titanium(III), chromium(II), silver(II) etc. and titrations in
molten salts can be performed.
5. In situ generation of titrants, for example electrolytic generation of iodine
used to estimate hydroquinone, ascorbic acid, antimony(III),
electrolytically generated bromine used to estimate organic substances
like oxine have been found to be the most satisfactory intermediates for
the estimation of several organic compounds.
6. Constant current coulometry has widely been used than the controlled
potential coulometry since the former is faster and requires simpler
instrumentation and less expensive.
7. Controlled potential coulometry is a quite sensitive method and has
selectivity.
 Types of Coulometry
1. Controlled potential coulometry: constant potential
is applied to electrochemical cell
2. Controlled current coulometry: constant current is
passed through the electrochemical cell
Faraday’s law:
Total charge, Q, in coulombs passed during
electrolysis is related to the absolute amount of
analyte:
Q = nFN
n = #moles of electrons transferred per mole of
analyte
F = Faradays constant = 96487 C mol-1
N = number of moles of analyte
Coulomb = C = Ampere X sec = A.s
• For a constant current, i:
Q = ite ; (
te = electrolysis time)

• For controlled potential coulometry: the current varies

with time:
t t e
Q=
t 0
i (t )dt

What do we measure in coulometry?

Current and time. Q & N are then calculated according
to one of the above equations
• Coulometry requires 100% current efficiency. What
does this mean?
– All the current must result in the analyte’s oxidation or
reduction
 Controlled potential coulometry
(Amperometry)
• The working electrode will be kept at constant
potential that allows for the analyt’s reduction
or oxidation without simultaneously reducing
or oxidizing other species in the solution
• The current flowing through the cell is
proportional to the analyt’s concnetration
• With time the analyte’s concentration as well
as the current will decrease
• The quantity of electricity is measured with an
electronic integrator.
Controlled potential coulometry
Instrumentation
Controlled potential coulometry
The instrumentation for potentiostatic coulometry consists of a potentiostat (to
maintain a constant potential), an electrolysis cell, a chemical coulometer or an
integrating device for determining the number of coulombs and placed in series
withthe working electrode. The chemical coulometer such as hydrogen-oxygen
coulometer/silver coulometer can be used to measure the number of coulombs
(quantity of electricity).
Cell Assembly
The cell assembly consists of a platinum gauze working electrode, a platinum wire
counter electrode and a saturated calomel electrode as the reference electrode. The
counter electrode is separated from the test solution by a porous tube containing the
same supporting electrolyte
Instrumentation
Controlled potential coulometry
Sometimes a mercury cathode is used instead of a platinum gauze electrode. This
cathode is useful for separating the easily reducible elements during an analysis. For
example, copper, nickel, cobalt, silver and cadmium are easily separated from ions
such as aluminium, titanium, alkali metals and phosphates. The precipitated
elements dissolve in mercury and form amalgams.

Potentiostat
A potentiostat is an electronic device which maintains the potential of the working
electrode at a constant level relative to a reference electrode.
Instrumentation
Controlled potential coulometry
Integrators
Most of the modern apparatus for potentiostatic coulometry employ integrators to
determine the number of coulombs required to complete an electrolysis.
Efficient stirring is important for controlled potential electrolysis, since all analyte
species must be swept up to the electrode surface, so that the electrochemical
reaction is completed. Besides stirring, the ratio of the electrode surface to solution
volume is another requirement of the experiment. This ratio plays a role in
determining the time needed for complete electrolysis, since the electrical current will
be directly proportional to electrode area, A and also directly proportional to the
concentration, c, of the analyte.
 Controlled potential coulometry
Applications
i) Inorganic Analysis
Controlled potential coulometric methods have widespread use in the determination of
several metal ions. As many as 55 elements of the periodic table can be determined by
the cathodic reduction of metal ions to metallic state. Most of the metals (about two
dozen element) can form amalgams with mercury, and hence controlled potential
coulometry with mercury cathode is usually preferred.
ii) Analysis of radioactive materials
The technique is widely adopted for the determination of uranium and pluotinum and
thus finds extensive use in the nuclear energy field. Reduction of UO + 2
2 to U4+ can be carried out in H2SO4 medium with a mercury pool cathode (− 0.6 V
vs. SCE). Samples containing 7 – 75 mg of uranium have been analysed with an
accuracy of ± 0.l %.
iii) Micro analysis
Controlled potential coulometry is more popular than the electrogravimetric methods
since it avoids the final step of weighing the product. The tedious process of drying
and weighing the electrode after each elecltrolysis is avoided. This technique is
especially useful for the determination of small amounts of analyte (0.01 – l mg) with
an accuracy of (± 0.5 %).
 Controlled potential coulometry
Applications
iv) Multistep controlled potential electrolysis
Determination of several metal ions in the same solution is possible with controlled potential electrolysis
using mercury pool cathode. A sample solution containing several metal ions such as Cu2+,
Bi3+,Pb2+,and Zn2+ can be analysed by controlled potential analysis. When the cathode potential is
controlled at about + 0.008 vs. SCE, Cu2+ is reduced to Cu0. When the current decays to zero, then the
potential can be controlled so that Bi3+ can be reduced to Bi0. Subsequently by controlling the potentials,
Pb2+ can be determined as Pb0
and Zn2+ as Zn. A sample of brass/bronze which contains Cu2+, Zn2+, and Pb2+ can be analysed by this
technique.
v) Continuous monitoring of gas streams
Determination of trace level concentration of oxygen in a gas stream can be done by controlled potential
analysis. The cell consists of a porous silver cathode and a cadmium anode. The reactions are

The porous silver cathode serves to break up the incoming gas into small bubbles, wherein
the reduction of oxygen takes place quantitatively within the pores. The hydroxyl ions formed
during reduction reacts with the cadmium anode and forms a Cd(OH)2(s) product.
 Controlled potential coulometry
Applications

vi) Electrolytic determination of organic compounds:

Controlled potential coulometry offers a new step for the electrolytic determination of organic
compounds. Trichloroacetic acid and picric acid are quantitatively reduced at a mercury
cathode. Coulometric methods permit the analysis of these compounds with an accuracy of
0.1%.

vii) Elctrolytic synthesis of new organic compounds :

Synthesis of new species and novel chemical compounds are possible. No chemical reagents
are required since electron itself is the reagent for carrying out these reactions. No
contamination of the products takes place.
viii) Determination of n-values of the reaction:
Controlled potential coulometry can be used to determine n values of the reactions.
Determination of n values offers a route to deduce the kinetics and mechanism of the
overall reactions. Picric acid is reduced at a mercury pool cathode, in which n value of
the reaction was found to be, l8. The reaction product is identified to be
triaminophenol.
 Coulometric Titration (Controlled-Current Coulometry)
• Coulometric titrations need an electrolytically generated titrant that reacts
stoichiometrically with the analyte to be determined. As in controlled-current coulometry,
100% current efficiency is required. The current is accurately fixed at a constant value and
the quantity of electricity can be calculated by the product of the current (in amperes) and
the time (in seconds) i.e. Q=I x t using endpoint detection.
• In principle, any endpoint detection system that fits chemically can be used; for example,
chemical indicators (color change), and potentiometric, amperometric or conductometric
procedures.
• For example the determination the amount of Arsenic oxide by titatration with Iodine. In
this titration to determine the concentration of a As 2O3(aq) solution, I2 is formed from KI at

generator electrode by an oxidation half reaction . The I 2 then reacts with the As2O3(aq).
 The moles of I2 formed is readily determined by measuring the current and the time
and recalling that one mole of electrons equals 96485 coulombs (amp seconds). One
particular advantage of this method is that I 2 is formed only as needed and hence all

the disadvantages of trying to store an I 2 solution are circumvented. The purpose of

this experiment is to determine the concentration of an unknown solution of
As2O3(aq).

Controlled-current coulometry maintains a constant current

throughout the reaction period. Here, an excess of a redox buffer
substance must be added in such a way that the potential does not
cause any undesirable reaction. That means the product of the
electrolysis of the redox buffer must react quantitatively with the
 Maintaining Current Efficiency
To maintain a constant current the cell potential must change until another
oxidation or reduction reaction can occur at the working electrode.
Unless the system is carefully designed, these secondary reactions will produce a
current efficiency of less than 100%.

• let's consider the coulometric

analysis for Fe2+ based on its
oxidation to Fe3+ at a Pt working
electrode in 1 M H2S04.
• Fe2+(aq) = Fe3+(aq) + e ‑
• The diagram for this system is
shown. Initially the potential of the
working electrode remains nearly
constant at a level near the
standard‑state potential for the Fe
3+
/Fe 2+ redox couple.
• As the concentration of Fe 2+
decreases, the potential of the
working electrode shifts toward more
positive values until another
oxidation reaction can provide the
necessary current.
• Thus, in this case the potential
eventually increases to a level at
which the oxidation of H2O occurs.
• 6H2O(l)  O2(g) + 4H3O+(aq) + 4e
• Since the current due to the oxidation of H2O does
not contribute to the oxidation of Fe2+, the current
efficiency of the analysis is less than 100%.
• To maintain a 100% current efficiency the products
of any competing oxidation reactions must react
both rapidly and quantitatively with the remaining
Fe2+.
• This may be accomplished, for example, by adding
an excess of Ce3+ to the analytical solution.
• When the potential of the working electrode shifts to
a more positive potential, the first species to be
oxidized is Ce3+.
• Ce3+(aq) = Ce4+(aq) + e‑
• The Ce4+ produced at the working electrode rapidly
mixes with the solution, where it reacts with any
available Fe2+.
• Ce4+(aq) + Fe2+(aq) = Fe 3+(aq) + Ce3+(aq)
• Combining these reactions gives the desired overall
reaction
• Fe 2+(aq) = Fe3+(aq) + e-
• Thus, a current efficiency of 100% is maintained.
• Since the concentration of Ce3+ remains at its initial
level, the potential of the working electrode remains
constant as long as any Fe 2+ is present.
• This prevents other oxidation reactions, such as that
for H2O, from interfering with the analysis.
• A species, such as Ce3+ which is used to maintain
100% current efficiency is called a Mediator.
 End Point Determination
• Adding a mediator solves the problem of maintaining 100% current
efficiency, but does not solve the problem of determining when the
analyte’s electrolysis is complete. Using the same example, once all the
Fe2+ has been oxidized current continues to flow as a result of the oxidation
of Ce3+ and, eventually, the oxidation of H2O. What is needed is a means of
indicating when the oxidation of Fe2+ is complete.
• Thus, the same end points that are used in redox titrimetry such as visual
indicators, and potentiometric and conductometric measurements, may be
used to signal the end point of a controlled-current coulometric analysis.
For example, ferroin may be used to provide a visual end point for the Ce3+
mediated coulometric analysis for Fe2+.
 Instrumentation
• Controlled‑current coulometry normally is carried
out using a galvanostat and an electrochemical cell
consisting of a working electrode and a counter
electrode.
• The working electrode is constructed from Pt, is also
called the generator electrode since it is where the
mediator reacts to generate the species reacting
with the analyte.
• The counter electrode is isolated from the analytical
solution by a salt bridge or porous frit to prevent its
electrolysis products from reacting with the analyte.
• Alternatively, oxidizing or reducing the mediator can
be carried out externally, and the appropriate
products flushed into the analytical solution.
 Coulometric Titration Instrumentation
• For coulometric titrations the instrumentation consists of a titrator
(constant-current source, integrator) and a cell. As the constant-current
source, an electronically controlled amperostat is preferably used. The
integrator measures the product of current and time (i.e., the number of
coulombs). The electrolysis cell, filled with the solution from which the
titrant will be generated electrolytically and the solution to be titrated
(analyzed), is schematically shown in Figure.
The generator electrode, at which the reagent is formed,
possesses a large surface area (e.g., a rectangular strip of
platinum). The auxiliary electrode (e.g., a platinum wire) is in
contact with an appropriate electrolyte of higher concentration
than the solution to be titrated. It is isolated from the analyte by
a sintered disk or some other porous media. This is required to
avoid the interference of additional products generated at the
second electrode. To circumvent these limitations of internal
generation, an external generator cell is often used.
Method for the external generation of oxidizing and reducing
agents in coulomtric titration
• The other necessary instrumental component for
controlled‑current coulometry is an accurate clock
for measuring the electrolysis time, te, and a switch
for starting and stopping the electrolysis.
• Analog clocks can read time to the nearest ±0.01 s,
but the need to frequently stop and start the
electrolysis near the end point leads to a net
uncertainty of ±0.1 s.
• Digital clocks provide a more accurate measurement
of time, with errors of ±1 ms being possible.
• The switch must control the flow of current and the
clock, so that an accurate determination of the
electrolysis time is possible.
 Coulometric Titration Applications

2.) Applications

a) Can be used for Acid-Base Titrations

- Acid titration
2H2O + 2e- » 2OH- + H2 titrant generation reaction

-
Base titration
H2O » 2H+ + ½ O2 + 2e- titrant generation reaction

b.) Can be used for Complexation Titrations (EDTA)

HgNH3Y2- + NH4+ + 2e- » Hg + 2NH3 +HY3-

HY3- » H+ + Y4-

c.) Can be used for Redox Titrations

Ce3+ » Ce4+ + e-

Ce4+ + Fe2+ » Ce3+ + Fe3+

3.) Comparison of Coulometric and Volumetric Titration
a) Both Have Observable Endpoint
- Current (e- generation)
serves same function as a standard titrant solution
- Time
serves same function as volume delivered
- amount of analyte determined by combining capacity
- reactions must be rapid, essentially complete and free of side reactions

b.) Advantages of Coulometry

- Both time and current easy to measure to a high accuracy
- Don’t have to worry about titrant stability
- easier and more accurate for small quantities of reagent
< small volumes of dilute solutions  problem with volumetric
- used for precipitation, complex formation oxidation/reduction or
neutralization reactions
- readily automated

c) Sources of Error
- variation of current during electrolysis
- departure from 100% current efficiency
- error in measurement of current
- error in measurement of time
- titration error (difference in equivalence point and end point)
 Advantages of Coulometric Titration
• Coulometric titrations possess some practical advantages:
• no standard solutions are required and unstable reagents can be
generated or consumed immediately,
• small amounts of titrants can be electrically quantified with high accuracy,
pretitration is possible, and the method can be readily adapted to
automatic remote control. Thus, with respect to controlled-potential
coulometry a wider field of practical applicaions exists. Often, automatic
titrators for multipurpose and single analysis employ potentiometric
endpoint detection. Examples are sulfur dioxide monitors and water
titrators (Karl Fischer).
• Controlled‑current coulometry, has two
advantages over controlled‑potential
coulometry.
– First, using a constant current leads to more rapid
analysis since the current does not decrease over
time. Thus, a typical analysis time for controlled
current coulometry is less than 10 min, as
opposed to approximately 30‑60 min for
controlled‑potential coulometry.
– Second, with a constant current the total charge
is simply the product of current and time. A
method for integrating the current‑time curve,
therefore, is not necessary.
Conductometry
 Conductometry
Conductometry is a kind of electroanalytical techniques based on
measuring electrolytic conductance.
Conductance

It is a measure of the ease with which current flows through a conductor.

The conductance G is defined as the reciprocal of the resistance
1
G
R
and is expressed in Siemens [S], that is in ohms-1 [Ω−1] or mhos. The
conductance of a homogeneous body of uniform cross section area is
proportional to the cross section area A and inversely proportional to the
length l :
A G
1 1 A
 .
G k R  l
l
where κ is the conductivity or the specific conductivity expressed in S·cm -
1
or in Ω−1·cm-1

137
 Conductivity or Specific conductance
Specific conductance or conductivity. It may be defined as the
conductance of a solution of 1 cm length and having 1 sq. cm
as the area of cross-section. In other words, specific
conductance is the conductance of
one centimetre cube of a
solution of an electrolyte.

constant has been found, conductivity can be calculated from

the experimental resistance by using equation 1


Specific conductance is defined by the number of the ions and
the their velocity. The more ion’s concentration and more their
velocity the more will be more conductance.
Therefore there are some factors that influence on the value
of κ: the nature of solvent and solute, the concentration of
electrolyte’s solution, temperature. 138
Resistance; It measures the obstruction to the flow of current.
The resistance of a conductor is proportional to the length (l)
and inversely proportional to the area of cross-section.

l
R  .
A

where ρ (rho) is the constant of proportionality and is called

specific resistance or resistivity. The resistance depends
upon the nature of the material. Its units are ohm (Ω )
R= ρ , if l =1 cm, a=1 cm2
In other words, specific resistance is the resistance between
opposite faces of one centimetre cube of the conductor.
 Conductometry
• Water itself is a very poor conductor of electricity, the
presence of ionic species in solution increases the
conductance considerably. The conductance of such
electrolytic solutions depends on the concentration of the
ions and also on the nature of the ions present ( through their
charges and mobilities ).
• Conductance behaviour as a function of concentration is
different for strong and weak electrolytes.
• Electrolytic solutions obey Ohm’s law just as metallic
conductors do. Thus the current i passing through a given
body of solution is proportional to the potential difference U,
and U
i
R
• where R is the resistance of the body of solution in ohms Ω .
140
 Molar Conductance
The conductivity of a solution depends on the concentrations
and mobilities of the ions present. It is convenient to define a
new quantity, the molar conductance Λ, by
1000

C
where c is the molar concentration, that is expressed in
mol·dm-3. 1000 is the factor arising from the fact that 1
dm3=1000 cm3. Thus, the molar conductance is expressed in
S·cm2·mol-1. The molar conductance is sometimes described
as the actual conductance of that volume of solution which
contains one mol of solute when placed between parallel
electrodes 1 cm apart with a uniform electric field between
them.

141
Equivalent conductance
It is defined as the conducting power of all the ions produced
by dissolving one gram equivalent of an electrolyte in solution.
It is denoted by the symbol (lambda).
1000
eq 
Ceq
Equivalent Conductance:
It is the conductance of one gram equivalent of solute
contained between two electrodes spaced one centimetre
apart.

Equivalent conductance K C = concentration in

  x1000
C gram equivalent / liter.

So as: the equivalent wt of the substances ↑

their equivalent conductances (λ) ↓
e.g. The λ of HCl (eq.wt. 36.5) is higher than NaCl
(eq.wt. 58.5)

Equivalent conductance is used to express the ability of

individual substance to conduct electric current.
From the previous equation it is clear that the equivalent
conductance increases as the concentration decreases
until it reaches a constant value at infinite dilution which is
known as:
Equivalent conductance at infinite dilution or
Limiting equivalent conductance, or
Mobility (λ∞). Which is the conductance of the
equivalent weight of the substance at infinite dilution.

It is characteristic for the solutes.

Equivalent ionic conductance:

At infinite dilution, interionic attractions become nil; the

overall conductance of the solution consists of the
sum of the individual equivalent ionic conductance.

Overall conductance = λ∞+ + λ∞-

λ∞+ is the equivalent ionic conductance of the cation at
infinite dilution.
λ∞- is the equivalent ionic conductance of the anion at
infinite dilution.
Equivalent ionic conductance differ according to the
nature of ions (i.e. Charge, size, hydration).
Cations λ∞ anions λ∞
H+ 350 OH- 198
Na+ 42.6 Cl - 76
K+ 74 NO 3- 71
NH4+ 73 CH 3COO- 41
Ag+ 62 propionate 36
½ Ba2+ 64 ½ SO42- 80
The conductance of electrolytic solutions
depends on:
1- Nature of ions:
The velocity by which ions move towards the
electrodes carrying the electric current varies
according to their nature (i.e. size, molecular
weight, number of charge the ion carries).
Velocity of ions α charge
α 1 / size
α 1 / molecular weight
α 1 / hydration
2- Temperature:

Conductance is increased by increase of temperature

as:
Energy of ions is increased &
viscosity and hydration are decreased.

An increase of temperature by 10C is accompanied by

2% increase in conductance.

for this reason the measurement must be carried out

at constant temperature using thermostatically
controlled conditions.
3- Concentration of ions:
 The electrical conductance of a solution is a summation of
contribution from all ions present.

 It depends on the number of ions/unit volume of solution and their

nature i.e. each ion represents itself independently.

 As the number of ions increases the conductance of the solution

increases.

 The linear relationship between conductance and c is valid only for

diluted solutions. In highly conc solu, there is interionic attraction
forces which decreases conductance.
But at infinite dilution, interionic attraction is negligible
and each ion represents itself independently.

At infinite dilution activity (a) equals concentration

(c) and activity coefficient a/c = 1, outside the infinite
dilution a/c < 1

So conductometric determination must be carried

out on dilute solution
4‑ The size of the electrodes:
Conductometric measurements are usually
carried out in a conductance cell, which
consists of two parallel sheets of platinum
(pt.) as inert electrodes.

The pt. electrodes must be platinized, i.e.

Covered by pt.black this will give large
surface area which will absorb tiny
quantities of electrode reaction products
produced during passage of current.
G α A, G α 1/L, G α A/L
G= K A/L
K is known as specific conductance or conductivity
it is the conductance when L is unity (1cm) and A is unity
(1cm2). OR it is the conductance of a one cubic cm of liquid
(1cm3).
K = G L/A (where L/A is known as cell constant)
The dimension of K is 1 / ohm.cm or ohm ‑1cm‑1 or
seimen/cm.
K, is a constant value for a specific solution. But it changes
with (is affected by) concentration, temperature and
change in cell constant.

N.B. For solution with high conductance(G) we use cells

with low A/L or high cell constant (L/A) and vice versa.
 INSTRUMENT USED IN CONDUCTOMETRIC DETERMINATION
To carry out a conductometric measurement it is necessary to measure
the resistance (R) of the solution and the conductance G= l/R
The instrument consists of two parts:
1‑ Conductance cell: A conductance
measuring cell consists of two inert electrodes
that face each other and immerse
in measuring solution. The inert electrode
is generally platinum or stainless steel.
The cross-sectional area corresponds
to the surface of electrodes and l is the
distance between them. .
2‑ Conductivity bridge (Kohlrausch bridge): A mean to measure the
resistance and then converts it to conductivity unit and It is formed of:
a‑ Wheatstone bridge.
b‑ An oscillator (to produce A.C. From D.C.).
The bridge is formed of:

A standard constant resistance R1. Rx

G
Unknown resistance (conductance
A B
cell) Rx.
C
R2 and R3 are formed of a uniform
cross section wire (AB) which is
divided to 100 equal parts it is N.B: The bridge is supplied
intersected by the sliding contact C by high voltage attached to an
which by changing its position will oscillator which change the
change both R2 and R3 (AC and CB). direct current (DC) to
alternative current (AC).
G is a galvanometer which acts as a WHY ?
current detector. to prevent electrolysis in the
cell and polarization of the
electrodes.
Now upon using the bridge:
the unknown cell is attached, Rx
the position of C will be
changed rapidly and G
automatically till the balance
A B
point , where no current is
detected. C
R1 Rx R1 R3
At balance  OR Rx 
R2 R3 R2
BC AB =100 part
OR R x  R1 AC = X
AC
CB = 100 – x
1 1 AC
G SO G  1. X
Rx R 1 BC G
R 1 (100  X)
 Application of Conductometry
1- Direct or Absolute Measurements:
 This is used in industry for checking the purity of distilled water
or other chemicals.
• Determination of physical constant such as ionization constant.
Determination of unknown concentration of pure substance:
where, a series of standard solutions of exact known
concentrations is prepared from pure grade of the substance to be
determined.
The conductance of the solutions
is measured and a calibration
curve is plotted representing the

Conductance
conductance against the concentration.
A solution of exact known
concentration of the substance to
be determined is prepared and
checked from the curve. Concentration
2- Indirect Conductometry
(Conductometric Titrations):
A conductometric titration involves measurements of the
conductance after successive addition of the titrant.

The end point is obtained from a plot of the conductance

against ml of titrant.

The most important advantages of this method are that it

can be used for determination of:
1-Turbid and highly colored solutions.
2-very dilute solutions
3-Reactions which are not complete and where is no suitable
indicator e.g. reaction between weak acid and weak base.
Precautions to be Considered in Conductomertic Titrations

1‑ Upon carrying out the titration; the titrant used must be at

least 10 times concentrated as the solution to be determined.
 e.g. on determination of solution 0.01 N HCl, the titrant
NaOH should be at least 0.1 N.
By this way, we can minimize decrease in conductance due
to dilution.
However a correction factor must be used to compensate for
this dilution.
Correction factor = Vi + Vt / Vi
Vi = initial volume of the solution.
Vt = titrant volume added.
2‑ Avoid the presence of external ions which
will not enter the reaction (such as the
presence of buffer or concentrated acids).
These ions will change the initial
conductance during the titration and can
not be accurately observed.

3‑ The method is suitable for detection of

end point in neutralization and
precipitation reactions but not for redox
reactions as there is no electron transfer
at the electrode surface.
I‑ Titration of Strong Acid with Strong Base: e.g. HCl ≠
NaOH
HCl + NaOH → NaCl + H2O
H+ + Cl- + Na+ + OH- → Na+ + Cl- + H2O
 Before titration the conductance is high which is due to HCl  H+ + Cl-
mobility of H+ is 350 and that of Cl- ion is 73.
 Upon addition of NaOH the H+ ion reacts with OH- ion to form the very
weakly ionized water molecule.
 This means that the H+ ion is removed from the medium and replaced by
Na+ ion which has a mobility of 43; thus a
continuous abrupt decrease in conductance
occurs during the titration till the end point. - H+ + OH-
+ Na + + Na+
 Beyond the end point there is excess Na +

and OH- ions with 43 and 198 mobility due to

continuous addition of NaOH
 So there is continuous increase in conductance E.p
and the curve will have a V shape , the end .

point is the minimum of the curve.

2- Titration of weak acid with strong base
e.g. CH3COOH ≠ NaOH

CH3COOH + Na+ + OH- → CH3COO- + Na+ + H2O

Before titration low initial conductance is observed due to low H+ obtained
during dissociation of weak CH3COOH.
During titration we can observe slight decrease of conductance due to
consumption of H+ .
During progress of titration we can
observe slight increase in conductance
due to the presence of CH3COO- (41) &
Na+ (43) and nearly constant H+ due to the + OH-
buffer action of the produced + Na+
CH3COONa and the remaining + CH3COO-
CH3COOH. + Na+
 After end point excess NaOH will lead to E.p
.
increase in conductance due to increasing
of Na+ (43) and OH- (198)
3- Mixture of strong acid and weak acid
aganist strong base.e.g. HCl/CH3COOH mix
≠NaOH

The initial conductivity is high it is due to HCl which by common

ion effect suppress the ionization of CH3COOH.
 Upon titration; decrease in conductivity occurs due to
replacement of H+ ion with mobility 350
by Na+ ion with mobility 43 , till all the H+
ions from HCl are neutralized.
CH3COOH will thus ionize and
react with NaOH.
The change in conductivity will take
place in similar way as described above. HCl e.p.
for acetic acid.
4- Precepitation Titrations

It is important to choose the suitable titrant which gives

sharp change at the equivalence point.

Titrant must have mobility that varies greatly from the

sample because the products are weakly ionizable
leading to decrease in conductance during titration till the
endpoint.
e.g. Titration of NaCl ≠ AgNO3
NaCl + AgNO3  AgCl + NaNO3
Na+ + Cl‑ + Ag+ + NO3‑  AgCl + NO3- + Na+

During titration of NaCl against AgNO3, Ag+ precipitate Cl- as

AgCl and NO3- replace Cl- in the medium.
As mobility of NO3- (71.5) is nearly equal that of Cl- (76.3) we
observe nearly no change in conductance during titration.
After complete precipitation of Cl- ,
+ Ag+
exx Ag (61.9) and NO3 (71.5) will
+ -
+ NO -
3

increase conductance of solution. - Cl

-

+ NO3-
 e.g. Titration of BaCl2 ≠ Na2SO4

BaCl2 + Na2SO4 BaSO4 +2 NaCl

Ba2+ + 2Cl‑ + 2Na+ + SO42‑  BaSO4 +2Cl‑ + 2Na+

During titration of BaCl2 against Na2SO4 , SO42- precipitate

Ba2+ as BaSO4 i.e1/2 Ba2+ (mobility 63.6 ) is replaced by Na+
(mobility 43), therefore conductance is decreased during titration.

After complete reaction conductance is

+ SO42-
increased due to addition of exx - Ba2+ + Na+
Na+ (43) and SO42- (mobility of ½ SO42- 80) + Na+

after the end point.

The curve is V shape its minimum is the
end point . It is obtained by extrapolation
of the two arms of the curve.
Thank you